Generation and analysis of mixed chlorinated/brominated homologs of the halogenated natural product heptachloro-1'-methyl-1,2'-bipyrrole

The 2,3,3′,4,4′,5,5′-heptachloro-1′-methyl-1,2′-bipyrrole (Q1, MBP-79) and further halogenated 1′-methyl-1,2′-bipyrroles (MBPs) are a class of marine natural products repeatedly detected in seafood and marine mammals from all over the world. Only Q1 is currently commercially available as reference standard and the full synthesis of mixed brominated-chlorinated compound is rather complicated. For this reason, synthetic Q1 (240 mg) was transferred into bromine-containing MBPs by UV-irradiation in the presence of bromine. Bromine, which rapidly vanished from the solutions, was re-newed during the reaction in order to generate higher amounts of Br-containing MBPs. A total of ∼150 mg Q1 was transferred after ∼10 min irradiation with high amounts of Br₂ to give 30.5 mg BrCl₆-MBPs along with lower proportions of Br₂Cl₅-, Br₃Cl₄-, Br₄Cl₃- and traces of Br₅Cl₂-MBPs. Longer UV-irradiation in the presence of Br₂ even allowed for the detection of Br₆Cl-MBPs and traces of Br₇-MBP. However, this reaction also provided some unknown by-products. A sample stored in the dark and later in in-door light (no UV irradiation) also eliminated Q1 after 76 d in favour of heptahalogenated MBPs with up to three bromine substituents. The irradiation products were separated on silica, and fractions containing only Q1 and BrCl₆-MBPs were then further fractionated by non-aqueous RP-HPLC. A pure isolate of the major BrCl₆-MBP (∼1.5 mg) was characterized by GC/MS and ¹³C NMR to be 2-bromo-3,3′,4,4′,5,5′-hexachloro-1-methyl-1,2′-bipyrrole (Br-MBP-75). Partial GC enantioseparation of the axially chiral Br-MBP-75 was achieved on a β-PMCD column. A full enantioseparation was managed by enantioselective HPLC using a NUCLEOCEL DELTA S column. Low amounts of pure BrCl₆-MBP enantiomers could be trapped.     

Comparison of atmosphere/aquatic environment concentration ratio of volatile chlorinated hydrocarbons between temperate regions and Antarctica

For the purpose of understanding the transport and deposition mechanisms and the air–water distribution of some volatile chlorinated hydrocarbons (VCHCs), their atmosphere/aquatic environment concentration ratio was evaluated. In addition, for the purpose of differentiating VCHC behaviour in a temperate climate from its behaviour in a polar climate, the atmosphere/aquatic environment concentration ratio evaluated in matrices from temperate zones was compared with the concentration ratio evaluated in Antarctic matrices.In order to perform air samplings also at rigid Antarctic temperatures, the sampling apparatus, consisting of a diaphragm pump and canisters, was suitably modified.Chloroform, 1,1,1-trichloroethane, tetrachloromethane, 1,1,2-trichloroethylene and tetrachloroethylene were measured in air, water and snow using specific techniques composed of a purpose-made cryofocusing-trap-injector (for air samples) and a modified purge-and-trap injector (for aqueous samples) coupled to a gas chromatograph with mass spectrometric detection operating in selected ion monitoring mode. The VCHCs were retrieved in all the investigated matrices, both Italian and Antarctic, with concentrations varying from tens to thousands of ng m⁻³ in air and from digits to hundreds of ng kg⁻¹ in water and snow.The atmosphere/aquatic environment concentration ratios were always found to be lower than 1. In particular, the Italian air/water concentration ratios were smaller than the Antarctic ones, by reason of the higher atmospheric photochemical activity in temperate zones. On the other hand, the Antarctic air/snow concentration ratios proved to be largely in favour of snow with respect to the Italian ratios, thus corroborating the hypothesis of a more efficient VCHC deposition mechanism and accumulation on Antarctic snow.     

超声波和零价铁联用对氯代苯酚脱氯降解作用的研究

采用超声波和零价铁联用对氯代有机物3氯苯酚(CP)、2,4-二氯苯酚(DCP)和2,4,6-三氯苯酚(TCP)模拟废水进行了脱氯处理研究。以单因素法, 考察了铁粉初始投加量、溶液的初始浓度、超声波功率和溶液的pH值等因素对氯代酚降解的影响,并探讨了降解反应动力学。结果表明,超声波和零价铁联用对氯酚具有显著的降解效果,当水样初始浓度为25 mg/L,溶液pH呈弱酸性,超声波功率为200 W时,氯代酚的脱氯效率达到最大值。降解反应符合准一级反应,CP、DCP和TCP的反应速率常数分别0.0613 h^-1、0.374 h^-1和0.197 h^-1。     

海河与渤海湾水体中溶解态多氯联苯和有机氯农药污染状况调查

在夏季对海河与渤海湾表层水中溶解态的多氯联苯（PCBs）和有机氯农药（OCPs）的污染状况进行了调查．结果表明,海河和渤海湾表层水中PCBs、六六六和滴滴涕的含量分别为0.06～3.11 μg/L、0.05～1.07 μg/L和0.01～0.15 μg/L．海河干流流域内的工业废水排放等陆源输入可能是渤海湾中PCBs和OCPs的重要来源．研究表明该地区PCBs与水中的DOC（dissolved organic carbon）具有一定的正相关．与国内外类似水体相比,海河中PCBs和OCPs污染情况较为严重,而渤海湾则处于中等水平．     

造纸厂土壤中短链和中链氯化石蜡的污染特征和风险评估

短链氯化石蜡是一类新型持久性有机污染物,氯化石蜡在造纸工业中常用作施胶剂,为了评估造纸厂区土壤中短链及中链氯化石蜡（SCCPs及MCCPs）的污染状况及其潜在风险,采集厂区表层和不同深度的土壤,利用全二维气相色谱-电子捕获负化学离子源-质谱（GC×GC-ECNI-MS）测定土壤中短链及中链氯化石蜡（SCCPs及MCCPs）的含量及同类物分布特征.结果表明,SCCPs和MCCPs在厂区土壤中均有检出,其含量分别为42~3853 ng·g^-1和34~2091 ng·g^-1,氯含量分别为59.9%~61.9%和48.7%~52.8%.不同采样点土壤样品中CPs（ΣSCCPs+ΣMCCPs）含量差异较大,污水处理区及施胶区土壤中SCCPs及MCCPs含量较高.与其他地区相比,厂区土壤中SCCPs及MCCPs处于较高水平.C₁₀Cl_6-7及C_14-15Cl₅是大部分土壤样品的主要同类物.主成分分析表明,厂区土壤中SCCPs及MCCPs可能主要来自于CP52产品的生产和使用.运用风险商值模型（RQ）评价SCCPs及MCCPs在造纸厂区土壤中的潜在风险,发现厂区土壤中SCCPs风险商范围为0.01~0.73,处于中等风险范围,MCCPs风险商范围为0~0.07,处于低等风险范围.儿童和成人人体暴露值低于TDI［10 μg·（kg·d）^-1］,造纸厂区非饮食暴露导致的健康风险较低.     

Ag/Fe催化还原体系处理水体中氯代烃的研究

研究了水体中的三氯甲烷(CF)、四氯化碳(CT)、1,1,1-三氯乙烷(1,1,1-TCA)、1,1,2,2-四氯乙烷(1,1,2,2-TeCA)、六氯乙烷(HCA)、三氯乙烯(TCE)、四氯乙烯(PCE)在Ag/Fe以及Fe⁰还原体系中的还原脱氯反应.结果表明,Ag的加入会明显提高氯代烃的还原脱氯速率,铁表面积浓度为150 m²·L^-1时,如果单独使用Fe⁰,CF、CT、1,1,1-TCA、1,1,2,2-TeCA、     

Determination of trace amounts of chlorinated insecticides and fungicides in ginseng using capillary gas chromatography and 63Ni electron capture detector

A method for the simultaneous determination of a series of chlorinated insecticides and fungicides as residues in ginseng is presented in this article. Pulverized samples are subjected to Soxhlet extraction with acetone-petroleum ether and the extract is partitioned between petroleum ether and aqueous sodium sulfate solution (2:98). The combined petroleum ether phase is cleaned up by sulfuric acid and analyzed by capillary gas chromatography using ⁶³Ni electron capture detector. Recoveries from the different concentrations for 11 kinds of chlorinated insecticides and fungicides are between 92.40 and 103.7% with coefficients of variations ranged 1.22 and 9.53% without samples, and between 89.00% and 104.10% with coefficients of variations between 1.16% and 9.16% with samples. The detection limits are 0.2- 7.0 ng/kg.     

有机化合物生物富集因子快速测定方法

本文运用二室模型，研究了挥发和非挥发性有机物在鲤鱼体内生物富集因子快速测定方法。     

Reductive Dechlorination of Tetrachloroethylene by Soil Sulfate-Reducing Microbes under Various Electron Donor Conditions

Biotransformation of tetrachloroethylene (PCE) by soil sulfate-reducing bacteria was investigated using acetate, lactate and methanol as electron donors. Results show that the effectiveness of biotransformation of PCE by soil sulfate-reducing bacterial is dependent upon the type of electron donor used.     

活性炭吸附-二硫化碳解吸-气相色谱法测定气态苯系物的实验室间比对分析研究

主要报告了全国24个环境监测实验室利用气态苯系物标准样品开展实验室间测量比对研究的结果,并提出了一套结果比较的统计评价方法.